PROCESS FOR PREPARING MELAMINE FROM UREA

PROCEDE DE PREPARATION DE MELAMINE A PARTIR D'UREE

English Abstract

Process for preparing melamine from urea at elevated temperature and in the
presence of a catalyst, in which a gaseous product stream is obtained which is
contacted with a liquid coolant in a cooling zone and in which a proportion of
the concentrated aqueous carbamate solution from the absorption zone is
returned to the cooling zone.

French Abstract

La présente invention concerne un procédé de préparation de mélamine à partir d'urée, à une température élevée et en présence d'un catalyseur. Selon ce procédé, un flux de produit gazeux obtenu est mis en contact avec un liquide de refroidissement, dans une zone de refroidissement, et une partie de la solution de carbamate aqueuse concentrée, issue de la zone d'absorption, est de nouveau conduite à la zone de refroidissement.

Claims

-6-
CLAIMS
1. Process for preparing melamine from urea at elevated temperature and in
the presence of a catalyst, in which a gaseous product stream is obtained
which is contacted with a liquid coolant in a cooling zone, characterized in
that a proportion of the concentrated aqueous carbamate solution from
the absorption zone is returned to the cooling zone.
2. Process according to Claim 1, characterized in that the gaseous product
stream coming from the reactor is cooled with a proportion of the
carbamate solution from the absorption zone, to which solution mother
liquor from the melamine purification and ammonia, carbon dioxide and
water condensed in the cooling zone may be added.
3. Process according to Claims 1-2, characterized in that 30-70% by weight
of the concentrated aqueous ammonium carbamate stream from the
bottom of the absorption zone is used for cooling the gas stream coming
from the reactor.
4. Process according to Claims 1-3, characterized in that the gas stream
coming from the quench columns or scrubbing section is cooled in a
condenser ahead of the absorption zone.
5. Process according to Claims 1-4, characterized in that the gas coming
from the reactor has a pressure of between 0.6 and 2.5 MPa.
6. Process according to Claim 5, characterized in that the gas coming from
the reactor has a pressure of between 0.7 and 2.2 MPa.
7. Technique for modifying existing melamine plants by applying the
process according to Claims 1-6.
8. Process as defined by the description and the example.

Description

CA 02398986 2002-08-01
WO 01/56999 PCT/NL01/00046
-1-
PROCESS FOR f'REPARING MELAMINE FROM UREA
The inventiori rFla~es to a process for preparing melamine from
urea at elevated temperature and in the presence of a catalyst, in which a
gaseous product stream is obtained which is contacted with a liquid coolant in
a
cooling zone.
A similar process is disclosed in for example WO-96/20933. This
describes the preparation of melamine by supplying urea and ammonia to a
reactor at a pressure of between 1.4 MPa and 2.0 MPa and a temperature high
enough for virtually complete conversion of urea into melamine in the presence
of
a catalyst. In the process there is obtained a gas stream containing melamine,
ammonia and carbon dioxide. In WO-96/20933 this gas stream is cooled with an
aqueous coolant in what is known as a quench pipe with evolution of a vapour-
liquid mixture, which mixture is virtually free from solid constituents. This
vapour-
liquid mixture is separated in this quench pipe into an aqueous melamine
product
stream and a vapour stream. The vapour stream from the quench pipe is
virtually
free from urea and melamine and consists essentially of ammonia, carbon
dioxide
and water vapour. The aqueous melamine product stream is virtually free from
solids and contains dissolved ammonia and carbon dioxide. After the dissolved
ammonia and carbon dioxide are removed with the aid of steam in a stripping
section, the aqueous melamine product stream is passed to the melamine
purification where the melamine is recovered. In this stripping section
evolves also
a vapour stream consisting essentially of ammonia, carbon dioxide and water
vapour. The vapour stream from the quench pipe, together with the vapour
stream
from the stripping section, is scrubbed in a scrubbing section with an aqueous
solution (mother liquor) from the melamine purification in order to remove
melamine residues still present in the vapour stream. This aqueous solution
may
contain ammonia, carbon dioxide and melamine. The quench pipe and scrubbing
section make up the cooling zone in the process according to WO-96/20933.
Next, the gas stream from the scrubbing section is passed to an absorption
zone
where it is contacted with an aqueous ammonia stream from the melamine
purification and liquid ammonia, in which process there is obtained a solution
of
concentrated aqueous ammonia and carbon dioxide (carbamate solution) and
ammonia vapour virtually free from water and carbon dioxide. In WO-96/20933,
this ammonia vapour is condensed and partly returned to the absorption zone,
the

CA 02398986 2002-08-01
WO 01/56999 PCT/NL01/00046
-2-
remainder after evaporation being used as fluidization gas for the reactor.
The
aqueous solution from the scrubbing section is passed to the quench pipe and
used as coolant there.
The concentrated aqueous carbamate solution from the
absorption zone, which WO-96/20933 reports contains 20-35 % by weight of
water, is for example supplied to a urea plant. Thus, in WO-96/20933 the gas
mixture coming from the reactor is cooled with the mother liquor from the
melamine purification, which liquor is passed to the quench pipe via the
scrubbing
section.
WO-96/20933 states that the water content of the carbamate
solution from the absorption zone is so low, i.e. 20 - 35 % by weight, that a
concentration step, in which water is removed from the carbamate solution, is
not
needed before the carbamate solution is supplied to a urea plant.
Experiments carried out by the applicant in accordance with the
process described in WO-96/20933 indicate, however, that it is advantageous to
remove water from the carbamate solution if the aim is to operate the
combination
of melamine plant and urea plant in the most economical manner.
In a melamine plant water is used among others as a component
of the liquid coolant. A proportion of the water eventually ends up in the
carbamate solution from the absorption zone which is supplied to for example a
urea plant.
Experiments and calculations by the applicant indicate that in the
process according to WO-96/20933 the amount of water in the carbamate stream
discharged to the urea plant is about 2.5 tonnes of water per tonne of
melamine.
In an economically optimum process, such as the Stamicarbon process described
in Nitrogen No. 139, Sep/Oct 1982, pp 32-39, in which the excess water is
removed in a concentration step, the amount of water in the carbamate solution
supplied to a urea plant is about 0.5 - 1.0 tonne of water per tonne of
melamine.
In the Stamicarbon process the gas mixture coming from the melamine reactor is
cooled with a liquid coolant in the quench columns. The mixture of vapour,
liquid
and, possibly, solid matter, is separated in the quench columns into a vapour
phase and a liquid phase. The vapour phase is passed to an absorption zone and
the liquid phase to the melamine recovery.
The aforementioned tonnes of water per tonne of melamine may
be converted to a water concentration in the carbamate solution from the
absorption zone, if the NH3/CO2 ratio of the carbamate solution exported is

CA 02398986 2002-08-01
WO 01/56999 PCT/NL01/00046
-3-
determined. If the plant according to WO-96/20933 is operated in an
economically
optimum manner, this ratio is minimum, for example 1.3 kg of NH3 per kg of
CO2.
This means that the water concentration in the carbamate solution from the
absorption zone in the process according to WO-96/20933 is 45 - 50% by weight.
In the aforementioned Stamicarbon process this is 20 - 25 % by weight.
For supplying this 45 - 50 % by weight of water-containing
carbamate stream to a urea plant it is economically attractive to further
concentrate the carbamate solution by removing water from this solution. The
drawback hereof is that this entails additional investments and that the
process
becomes more costly due to increased usage of steam, cooling water and
electricity.
It has been found that this drawback can be overcome by
returning a proportion of the concentrated aqueous carbamate solution from the
absorption zone to the cooling zone. In particular, a proportion of the
concentrated
aqueous carbamate solution from the bottom of the absorption zone is returned
to
the cooling zone.
In WO-96/20933 this cooling zone is made up of the quench
pipe and the scrubbing section; in the Stamicarbon process this cooling zone
consists of the quench columns. In both processes, the remainder of the
concentrated aqueous carbamate solution from the absorption zone is supplied
to
for example a urea plant, preferably a high-pressure section of a urea plant,
without any further processing.
In an embodiment of the invention the gas stream coming from
the quench columns or the scrubbing section is cooled in a condenser ahead of
the absorption zone. Here, the gas stream is cooled by at least 50C,
preferably at
least 10 C and in particular at least 15 C. The dilute carbamate solution
coming
from the condenser ahead of the absorption zone is passed to the cooling zone.
In
this condenser evolves a gas which is enriched with ammonia and carbon dioxide
and which is passed to the absorption zone. In the absorption zone then
evolves a
concentrated aqueous carbamate solution which contains less water and which is
partly returned to the cooling zone.
The liquid coolant preferably consists of an aqueous carbamate
solution composed of a proportion of the concentrated aqueous carbamate
solution from the absorption zone to which mother liquor from the melamine

CA 02398986 2002-08-01
WO 01/56999 PCT/NLOl/00046
-4-
purification (backend section) may be added, and ammonia, carbon dioxide and
water condensed in the cooling zone.
20-40% by weight of the gas going to the absorption zone is
returned in condensed form to the cooling zone. In the specific case where the
bottom product from the absorption zone is returned, this means that 30-70% by
weight of the concentrated carbamate solution from the absorption zone is used
for cooling the gas stream coming from the reactor and preferably 35-65% by
weight. The remainder is supplied to for example a urea plant but may also be
used for other purposes such as a fertilizer plant or production of ammonia.
It has been found that in the process of the invention the water
content of the concentrated carbamate solution from the absorption zone
eventually amounts to 20-35% by weight. This does render the proportion of
this
carbamate solution which is retumed to a urea plant suitable for direct
processing.
This means that the concentration step is superfluous.
Furthermore, it was found that the process of the invention is
particularly suitable for so-called gas-phase melamine plants operating at a
pressure of 0.6-2.5 MPa, more particularly at pressures of between 0.7 MPa and
2.2 MPa.
The process of the present invention is particularly suitable for
modifying existing melamine processes such as those described in WO-96/20933
and the Stamicarbon process as described in the aforementioned Nitrogen
publication.
The invention is illustrated by the following examples.
Examples I - III
Melamine was prepared in a cylindrical fluidized bed with an
inside diameter of 1 metre and a height of 15 m. The catalyst was fluidized by
introducing ammonia through a gas distribution plate and was heated by heat
exchanger tubes in the reactor through which molten salt flowed. Liquid urea
was
sprayed into the reactor with the aid of a two-phase sprayer using ammonia as
atomizing gas. The reactor was operated at 390 C and a total pressure of
0.7 MPa (Example I), 1.7 MPa (Example II) and 2.0 MPa (Example III). Urea was
metered at the rate of 1.4 tonnes/hour with 0.7 tonne of ammonia per hour via
the
two-phase sprayers. Ammonia was supplied through the fluidization plate at the
rate of 0.7 tonne/hour. The conversion of water-free urea to melamine relative
to

CA 02398986 2007-05-16
22772-1459
-5-
equiEibriurn was higher than 9F %. The gas stream from the reactor contained
NH;,
CO2, melamine vapour and traces of by-products and was cooled in the cooling
zone with liquid coolant. A proportion of the concentrated aqueous carbamate
solution from the absorption zone was retumed to the cooiing zone. The
remainder of the concentrated carbamate soiution was supplied to the adjacent
urea plant. The proportion of the carbamate from the absorption zone that was
returned to the cooling zone and the amount of water in the carbamate stream
from the absorption zone are stated in Table 1
Comparative example A
Analogously to Examples I-- Ill, malamine was prepared except
that no carbamate from the absorption zone was retumed te the coofing zone.
The
carbamate stream coming from the absorption zone was then too dilute for it to
be
supplied to a urea plant without an intermediate step. Refer to Table 1.
Table 1
Example I II III A
Pressure in Mpa 0.7 1.7 2.0 1.7
Proportion of carbamate from absorption 5 6 51 50 0
zone returned to cooling zone in % by
weight
VUater content of carbamate from 28 25 24 49
absorption zone in % by weight
Amount of exported water in kg per kg of 0.89 0.74 0.70 2.5
melamine
SECTION 8 CORRECTION
SEE CERTIFICATE
CORRECTION. ARTICLE 8
VOIR CERTIFICAT